Furyl amine derivatives



Patented 14,1939

UNITED, STATES PATENT OFFICE.

FURYL AMINE nemvarrvns Howard L Cramer, Cuyahoga Falls, Ohio, assignor .to Winzfoot Corporation, Wiimi flon, M, a corporation oi Delaware I No Drawing.

Application November 5, 1934, Serial No; 151,591

10 claims. (Cuzco-34s) This invention relates to a new class of compounds which may be called carbon bisulphide derivatives of amines containing a furane ring. The compounds are simply prepared and are val- 5 uable as accelerators of the vulcanization of rubber.

The invention resides in the discovery of compounds which are illustrated by the formula M'representing metal, ammonium, substituted ammonium, dinitro' aryl, aryl methylene, the B i 15 s-c-n or the group and R. in all instances representing an amino group containing a furane ring. Typical of such materials are (1) The metal salts of iurfuryl dithiocarbamates sucli as, for example, zinc ethyl alpha fur- 25 furyl dithiocarbamate. having the formula;

30. (2) The ammonium salts such as, for example,

di(alpha i'uri'uryl) ammonium di(alpha iuriu'ryl) dithiocarbamate having the formula:

(s) The thiuram disulphides such asfior example, dibutyl di(alpha i'uri'uryl) thiuram disulphide having the formula .ne---'cn' s s nc- --cn al -crn-ns-h-ii-n-Om-ii (in H. I I 4H; O

' 45 4) The thiuram monosulphidee such as, for

example, tetra (alpha furfuryl) thiuram mono sulphide having the formula:

Others are dinitro phenyl di(alpha furiuryl) dithiocarbamate and phenyl methylene (benzal) i bis di(alpha iuriuryl) dithiocarbamate. 5 The methods of preparation or these new. di-

- thiocarbamic acid derivatives are simiiar'to those employed for known dithiocarbamic acid derivatives. Thus, the substituted ammonium salts may be prepared by treating two mole of the desired amine containing a furane ring with one 5 mol of carbon disulphide in an inert solvent, such as gasoline or petroleum ether, from which the salts readily precipitate. The metallic salts are preferably prepared by the addition of a soluble salt of a metal to an aqueous solution of the sodium dithiocarbamate, the latter being prepared bytreating one mol of the amine containing a furane ring with one mol of carbon disulphide and one mol of sodium hydroxide in 'aque- The thiuram disulphide maybe ous solution.

conveniently prepared by the oxidationof the sodium salt of the dithiocarbamate in aqueous solution with ammonium persulphate. The thiuram' mono sulphide may he prepared from the thiuram disulphide by desulphurizing the latter by treating it in alcohol solution with one mol of potassium cyanide. The dinitrophen'yl esters are prepared by adding to a ,molar quantity of the sodium dithiocarbamate in alcohol or water one mol of dinitro chlor benzene in warm alcohol. The phenyl methylene (benaal) derivative is preparedsimilarly by reacting thesodium dithiocarbamate with benzal chloride and heating the mix ture to 60-70" C. for a short time.

The amines containing a turcne ring applicable 3 for. use in the practice of the invention may be represented by the general formula 1 I wherein R." is a radical containing a iurane ringand R" is a monovalent radical such as hydrogen or alkyl, alicyclic. iuriuryl or aralkyl groups. In

general, any primary or secondary amine contain- 40 ing a iurane ring and in which aliphatic characteristics predominate may be employed in the practice or the invention.

Illustrative of amines containing a iuranering. and di alphaand betaiuriuryl amines, di alphaand betafuryl amines, N-ethyl alphaand betaiuriuryl amines, N-cyclohexy l aiphaand beta iuriuryl amines, N-benzyl alphaand betafurfuryl' amines, di(alphaor beta- 2-furyl ethyl) amineaN-methyl alpha and the N-hexahydro tolyl alpha furiu'ryl amines.

Further exemplary oi the invention are the 55 turturyl amine, N-iso butyl alpha furiuryl amine, N-beta phenyl ethyl- ,ene alpha 'ruriuryl amine, N-iso propyl alpha turiuryl ,amine, N-iso amyl alpha iurfuryl amine,

following tables describing the properties illustrative examples. Table I gives the melting points, if a solid compound, and the colors of the compounds. Table II gives the nitrogen, sulphur and metal, if any, contents for the com- .pounds as compared with the theoretical percentages.

Table I Compound g Color 1 Di(aipha furluryi) ammonium di(a1pha Oil Yellow.

iurluryl) dithiocarbamate. 2 Zincdi(alphafurfuryl)dithiocarbamate 190-3...- White. 3 Leaddi(alphafuriuryl)dithiocarbamate. 130-1 Buff. 4 Tetra (alphaiuriuryl) thiuram disulphide .Oil Brown. 5 Tetra (alpha iuriuryl) thiuram mono sul- Oil Do.

phide.

Table II Analyses in percent cal- Found culated Com-* pound Nitrogen Sulphur Metal Nitrogen Sulphur Metal 45 hexyl dl(alpha furfuryl) thiuram diand mono- CERTIFICATE Patent No. 2,150,1 3.

sulphides, dlethyl di(alpha furiuryl) thiuram diand monosulphides,-dibenzyl di alpha furfuryl thiuram diand mono sulphides, dimethyl di(alpha Iurfuryl) thiuram diand monosulphides, di hexahydro tolyl di(alpha furfuryl) thiuram diand monosulphides and di (beta phenyl ethylene) di(alpha furfuryl) thiuram diand monosulphides.

It is intended that the patent shall cover, by suitable expression in the appended claims, whatever Ieatures of patentable novelty reside in the invention.

What I claimis:

l... A normal zinc salt of a dithiocarhamlc acid in which the nitrogen atom of the dithiocarbamic acid group is attached to a radical selected from the group consisting of furo, furomethylene and furoethylene radicals.

2. An amine salt of a 'dithlocarbamic acid in which the nitrogen atom oi the dithiocarbamic acid group is attached to a radical selected from the group consisting of furo, furomethylene and furoethylene radicals.

3. Zinc di-N-N-(alphafuromethylene) 'dithiocarbamate.

4. Di-N-N'-(aiphafuromethylene) ammonium di-N-N-'(alphafuromethylene) dithiocarbamate.

5. A normal metal salt of an N-hydrocarbon N-alphafuromethylene dithiocarbamlc acid.

6. A binary alphafuromethylene ammonium N -hydrocarbon N-alphafuromethylene dithiocarbam'ate. A

7. A. normal bivalent metal salt of di-N-N- (alphafuromethylene) dithiocarbamic acid.

8. An ammonium salt of an N-hydrocarbon N -alphafuromethylene dithiocarbamic acid.

9. A normal zinc salt of an N-hydrocarbon OF CORRECTION.

' March 1h, 1959..

HOWARD I. CRAMER. a It is hereby certified that error appears in the. printed specification of the above nuinberedpatent requiring correction as follows: Page 1, second column, n 145, for the word "and" first occurrence, read are; page 2, first column, lines 7+2 and 1. .5, for "thiocarbemate.

Others are di morpholyl" read dithiocarbamate. Others are morpholyl; and that he said Letters Patent should be read with this correction therein that the same may confor n t0 the record of the case .inthe Patent Office.

Signed and sealed this 16th day of May. A. 13... 1959.

(Seai) i-lenr yj Van Arsdale hating Commissioner of Patents. 

